JPH0333847A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To accelerate desilvering and to inhibit bleach fogging by using a bleaching soln. of a specified pH contg. an oxidizing agent having a specified oxidation-reduction potential or above. CONSTITUTION:A bleaching soln. of pH 2.5-4.2 contg. an oxidizing agent having >=150 mV oxidation-reduction potential is used. When a sensitive material enters the bleaching soln. after color development, pH in the film of the sensitive material lowers. In the case where the pH lowers rapidly, bleach fogging is inhibited. In the case where the pH lowers slowly or the pH of the bleaching soln. is high, bleach fobbing is increased. The bleaching agent having >=150 mV oxidation reduction potential is used so as to obtain satisfactory oxidizing power and to enable rapid bleaching. Bleaching is accelerated and bleach fogging can be prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for processing silver halide color light-sensitive materials.

<Prior Art> Silver halide color photosensitive materials (hereinafter referred to as color photosensitive materials) are processed through steps such as color development, desilvering, water washing, and stabilization after exposure.

Color developer for color development, bleach, bleach-fix, and fixer for desilvering, tap water or ion exchange water for washing,
Stabilizing solutions are used in each stabilization process. The temperature of each processing solution is usually adjusted to 30 to 40 DEG C., and the color photosensitive material is immersed in these processing solutions to be processed.

Among these processing steps, the basic ones are a color development step and a desilvering step.

In the color development step, exposed silver halide is reduced by a color developing agent to yield silver, and the oxidized color developing agent reacts with a color former (coupler) to provide a dye image.

In addition, in the desilvering step that follows this color development step, the silver produced in the color development step is oxidized by the action of a bleaching agent, which is an oxidizing agent, and then dissolved by a fixing agent, which is a complex ion forming agent for silver ions. Only a dye image is formed.

The above desilvering process includes a method in which the bleaching process and the fixing process are performed in the same bath, a method in which the process is performed in separate baths, and a method in which the bleaching process and the bleach-fixing process are performed in separate baths. Moreover, in this case, each bath may be multi-tank.

In addition to the above-mentioned basic steps, various auxiliary steps are performed for the purpose of maintaining the photographic and physical quality of the dye image or improving its shelf life. Such a step is carried out using, for example, a hardening bath, a stop bath, an image stabilizing bath, a water washing bath, and the like.

<Problems to be Solved by the Invention> In recent years, with the spread of small in-store processing service systems called minilabs, there has been a strong demand for faster processing.

In particular, the time required for the desilvering process conventionally occupies most of the processing time required for the entire process, and there is a desire to shorten this desilvering process time.

However, the ferric complex salt of ethylenediaminetetraacetic acid, which is mainly used as a bleaching agent in bleaching solutions and bleach-fixing solutions, has a fundamental drawback of weak oxidizing power. Although improvements have been made, the above requirements have not yet been met.

On the other hand, bleaching agents with strong oxidizing power include red blood salt, dichromate, ferric chloride, persulfate, and bromate, etc. Each of them has many drawbacks from the viewpoint of performance and the like, and cannot be widely used for over-the-counter processing.

Among these, for example, JP-A No. 62-222252 discloses a bleaching solution with p)I of about 6 containing a ferric complex salt of 1,3-diaminopropanetetraacetic acid having a high oxidizing power.

Further, JP-A No. 64-24253 also discloses a bleaching solution (for example, pH 5.0) containing a ferric complex salt of 1,3-diaminopropanetetraacetic acid.

This product enables more rapid silver bleaching compared to bleaching solutions containing ferric ethylenediaminetetraacetic acid complex salts, but in particular, if bleaching is performed directly after color development without using an intermediate bath, the bleaching fog will be reduced. A major problem is the occurrence of color fog called .

In the desilvering process, a method in which the bleaching step and fixing step are performed separately in separate baths requires a larger number of baths than a method in which bleaching, which is an oxidation reaction, and fixing, which is a reduction reaction, are performed in the same bath. It has the advantage of being able to process things stably.

Furthermore, a method in which a bleaching step and a bleach-fixing step are combined and each step is performed in separate baths is attracting attention as a method that promotes desilvering (Japanese Patent Application Laid-open No. 75352/1983).

In such a method using two baths, it is necessary to consider not only speeding up the bleaching process, but also speeding up the subsequent fixing process and bleach-fixing process. cannot be said to have been adequately addressed yet.

A first object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material, which enables rapid desilvering, is free from bleaching edge blur, and has excellent desilvering properties.

A second object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material, which achieves the first object and is capable of preventing stains on the surface of the light-sensitive material.

Means for Solving the Problems> In order to achieve the above object, the present invention has the following configuration (1).
(2).

(1) After imagewise exposure of the silver halide color photographic light-sensitive material,
In a processing method in which a color development process is performed with a color developer containing an aromatic primary amine color developing agent, and then a bleaching process is performed with a bleaching solution, the bleaching solution has an oxidation-reduction potential of 150
Contains an oxidizing agent of mV or more, and the pH of this bleaching solution is 2.
．． 5 to 4.2. A method for processing a silver halide color photographic light-sensitive material.

(2) A method for processing a silver halide color photographic light-sensitive material, which comprises bleaching with a bleaching solution in the above (1) and then processing with a processing solution having a fixing ability and containing thiocyanate as a fixing agent.

According to the present invention, since the bleaching process is performed using a bleaching solution containing an oxidizing agent with a redox potential of 150 mV or more and a pH of 2.5 to 4.2, the bleaching process can be performed quickly. In addition, it is possible to eliminate the occurrence of bleaching blade burrs.

In addition, in the treatment using a treatment solution having fixing ability following the above bleaching treatment, if a treatment solution containing thiocyanate as a fixing agent is used, the treatment can be further accelerated and It also has excellent silver properties.

For this reason, the entire desilvering process can be speeded up, and the photographic properties are also good.

In addition, it is stated that when a fixing solution containing thiocyanate in addition to thiosulfate is used as a fixing agent during one-bath processing of black and white photosensitive materials, the clearing time becomes shorter, that is, the fixing speed increases. has been done (G
Written by rant HaistModern Photogr
aphic Processing Vol. 2 p171) Regarding the processing of 2nd Cap 171 materials, a bleach-fix solution using a combination of thiosulfate and thiocyanate is described (ibid., 9583). This is only for processing solutions that have fixing ability, such as fixing solutions and bleach-fixing solutions, and does not deal with speeding up desilvering processing including bleaching processing, as in the present invention. No methods are presented for solving the problem of deterioration in photographic performance caused by speeding up processing. Therefore, it does not imply the present invention.

Specific composition> Hereinafter, a specific configuration of the present invention will be explained in detail.

In the method for processing a silver halide color photographic light-sensitive material (hereinafter also referred to as "light-sensitive material") of the present invention, the light-sensitive material after imagewise exposure is color-developed and then bleached.

During this bleaching process, the bleaching agent, which is an oxidizing agent contained in the bleaching solution used, has an oxidation-reduction potential of 150 + aV or more,
Preferably 180 mV or more, more preferably 200 mV
That's all.

The redox potential of the bleach mentioned above is determined by the Transactions of the Faraday Society (Tra
actions of the FaradayS
55 (1959), 1312~
It is defined by the redox potential measured by the method described on page 1313.

The redox potential in this case was obtained by the method described above under the condition of pH 6.0.

The reason why the potentials determined at pos and o are used is that pH around 6.0 is a standard for the occurrence of bleaching blade burrs.

In other words, the present inventors have actually found that when the color development process is completed and the photosensitive material enters the bleaching solution, p in the film of the photosensitive material is
H decreases, but if the pH decreases quickly at this time, the bleaching edge will be small, and if the pH decreases slowly, the r
It has been confirmed that bleaching fog increases when It+ is high, and based on these facts, poe and o are used as standards.

In the present invention, a bleaching agent having a redox potential of 150 mV or more is used because such a bleaching agent can provide sufficient oxidizing power and can perform a rapid bleaching process.

Such bleaching agents include inorganic compounds such as red blood salt, ferric chloride, dichromate, persulfate, and bromate, and some organic compounds such as aminopolycarboxylic acid iron (III) complex salts. can be mentioned. In the present invention, it is preferable to use an aminopolycarboxylic acid iron(III) complex salt from the viewpoints of environmental protection, handling safety, metal corrosivity, and the like.

Below, the aminopolycarboxylic acid iron (In
) Specific examples of complex salts will be given, but the invention is not limited to these. In addition, the redox potential in the above definition will be described.

Compound no.

Redox potential (mV vs, NHE, p! (=6) 1, N-(2-acetamido)iminodiacetic iron (III) complex salt 2, Methyliminodiacetic iron (m) t! salt 3, iminodiacetic iron (III) Complex salts 4.1.4-Butylenediaminetetraacetate iron(III) complex salt 5, diethylenethionythyldiaminetetraacetate iron(III) complex salt 6, glycol ether diaminetetraacetate iron(III) complex salt 7.1.3-propylene Diaminetetraacetic acid iron (rn) complex salt 80 00 10 30 30 40 50 Among these, particularly preferred are compound No.
7 of 1,3-propylenediaminetetraacetic acid iron(III)
It is a complex salt (hereinafter abbreviated as 1,3-PDTA-Fe(III)). It is the same compound as iron(m) complex salt).

Aminopolycarboxylic acid iron (III) complex salts are used in the form of sodium, potassium, ammonium, etc. salts, but ammonium salts are preferred because they bleach the fastest.

In addition, ethylenediaminetetraacetic acid iron(III) complex salt (EDTA-Fe(III)) widely used in the industry is 1
10 mV, iron diethylenetriaminepentaacetate (m)
i salt, trans-1,2-cyclohexanediaminetetraacetic acid iron(III) salt, etc. have a voltage of 80 mV, and are excluded from the present invention.

The amount of bleach used in the bleaching solution in the present invention is 1
It is preferably 0.10 mol or more per β, and 0.15 mol or more is preferable in terms of speeding up the processing and reducing bleaching blade blur and stain.

Particularly preferred is 0.25 mol or more.

However, since the use of an excessively high concentration solution will actually inhibit the bleaching reaction, the upper limit of the concentration is preferably about 0.7 mol.

Note that iron(III) aminopolycarboxylate is preferably used in the present invention! The concentration of the salt is also preferably within the above range.

Further, in the present invention, bleaching agents may be used alone or in combination of two or more.

When two or more types are used together, the total concentration may be within the above range.

Furthermore, in the present invention, the redox potential is 150 mV.
In addition to the above bleaching agents, bleaching agents having an oxidation-reduction potential of less than 150 mV may be used in combination. However, the amount used is 0.5 per mole of bleach with an oxidation potential of 150 mV or more.
It is preferable to set it to about molar or less.

Such substances include, in particular, iron(III) aminopolycarboxylate with a redox potential of 150 mV or more! ! When used in combination with a salt, examples include ferric complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and cyclohexanediaminetetraacetic acid.

When using an aminopolycarboxylic acid iron (III) complex salt in a bleaching solution, it can be added in the form of a complex salt as described above, but if the complex-forming compound aminopolycarboxylic acid and ferric salt (e.g. , ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate> may be present in the bleaching solution to form a complex salt.

In the case of this complex formation, the aminopolycarboxylic acid may be added in a slightly excess amount compared to the amount required for complex formation with ferric ions, and when added in excess, it is usually 0.01.
It is preferable to use an excess in the range of 10% to 10%.

The bleaching solution containing a bleaching agent having an oxidation-reduction potential of 150 mV or more in the present invention has a phl of 2.5 to 4.2, preferably 2.5 to 4. Particularly preferred is 2.5 to 3.6.

By setting the pH in this range, it is possible to speed up not only bleaching but also desilvering, including processing with a processing solution having fixing ability in the next step.

At this time, if the pH is less than 2.5, although it is effective in reducing the bleaching blade brittleness and speeding up the processing, it is not realistic to achieve such a low pH, and conversely, the bleaching solution There are disadvantages such as deterioration of the solubility of the bleach replenisher and precipitation at low temperatures, and, on the other hand, when the pH exceeds 4.2, bleach blade blur increases significantly.

Furthermore, in Japanese Patent Application Laid-open No. 62-222252, 1.3-DP
A pH 6 bleach solution containing TA-Fe (III) is disclosed.

In addition, conventionally, bleaching solutions containing aminopolycarboxylic acid iron ([) complex salts have been widely used, and the pH of such bleaching solutions is as follows:
In either case, a pH of around 5 to 6 is considered optimal in terms of both ensuring the bleaching speed and preventing poor recoloring of the cyan dye, and such pH is widely practiced. This is because although lowering the pH increases the bleaching rate, it has been thought that cyan dye recoloring is impaired.

However, in the present invention, even when the pH is in the range of 2.5 to 4.2, the cyan dye does not suffer from poor color restoration, and the above-mentioned effects of the present invention are obtained, which is unexpected. It is.

In the present invention, a bleaching solution used for bleaching treatment contains a bleaching agent having an oxidation-reduction potential of 150 mV or more, and the p
By setting H to 2.5 to 4.2, the effects of speeding up the bleaching process and reducing bleaching blade blur can only be obtained, and this cannot be achieved even if any of the requirements are missing. do not have.

In the present invention, known acids can be used to adjust the pH to the above range.

As such an acid, an acid having a %pKa of 2 to 5 is preferable.

In the present invention, pKa represents the logarithm of the reciprocal of the acid dissociation constant, and the ionic strength is 0. The values determined at 1 mol/j and 25°C are shown.

In the present invention, it is preferable to use a bleaching solution containing 1.2 mol/1 or more of an acid having a pKa in the range of 2 DEG to 5.0 in the desilvering step.

By containing 1.2 mol/1 or more of an acid with a pKa of 2.0 to 5.0 in the bleaching solution, it is possible to further eliminate bleaching blade blur and improve the increase in stain in uncolored areas after treatment. .

The acid with a pKa of 2.0 to 5.0 may be an inorganic acid such as phosphoric acid, or an organic acid such as acetic acid, malonic acid, or citric acid.
Acids between 2.0 and 5.0 are organic acids. Among organic acids, organic acids having a carboxyl group are particularly preferred.

The organic acid having a pKa of 2.0 to 5.0 may be a monobasic acid or a polybasic acid. In the case of a polybasic acid, if its pKa is within the above range of 2.0 to 5.0, it can be used as a metal salt (eg, sodium or potassium salt) or ammonium salt. Further, two or more kinds of organic acids having a pKa of 2.0 to 5.0 can be used in combination. However, aminopolycarboxylic acids and their Fe complex salts are excluded.

Preferred specific examples of organic acids with a pKa of 2.0 to 5.0 used in the present invention include formic acid, acetic acid, monochloroacetic acid,
Aliphatic-basic acids such as monobromoacetic acid, glycolic acid, propionic acid, monochloropropionic acid, lactic acid, pyruvic acid, acrylic acid, butyric acid, isobutyric acid, bivaric acid, aminobutyric acid, valeric acid, isovaleric acid: asparagine, Amino acid compounds such as alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine, and leucine; Aromatic-basic acids such as benzoic acid and monosubstituted benzoic acids such as chloro and hydroxy, and nicotinic acid;
Aliphatic tribasic acids such as oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, glutaric acid, adipic acid: aspartic acid, glutamic acid, glutaric acid, cystine, ascorbic acid Various organic acids can be listed, such as amino acid dibasic acids such as; aromatic tribasic acids such as phthalic acid and terephthalic acid; and polybasic acids such as citric acid.

In the present invention, among these, monobasic acids having a carboxyl group are preferred, and acetic acid and glycolic acid are particularly preferred.

In the present invention, the total amount of these acids used is 1.2 mol or more per 2 bleaching solutions. Preferably 1.2 to 2.5
Mol/l. More preferably, it is 1.5 to 2.0 mol/Il.

When adjusting the pH of the bleaching solution to the above range, use the above acid and alkaline agent (e.g. aqueous ammonia, KOH% NaOH).
may be used together. Among them, ammonia water is preferred.

Various bleach accelerators can be added to the bleach solution of the present invention or its prebath.

Such bleach accelerators are described, for example, in US Pat. No. 3,893,858, German Patent No. 1,290.
, 8L2 specification, British Patent No. 1,138,842, JP-A-53-95630, Research Disclosure No. 17129 (July 1978 issue) having a mercapto group or a disulfide group. Compounds, thiazolidine derivatives described in JP-A No. 50-140129, thiourea derivatives described in U.S. Pat. No. 3,706,561, iodides described in JP-A-58-16235, German patents Polyethylene oxides described in Specification No. 2,748,430, Japanese Patent Publication No. 1973-
Polyamine compounds described in Japanese Patent No. 8836 can be used. Particularly preferably British Patent No. 1,138
, 842 are preferred.

In addition to bleaching agents and the compounds mentioned above, the bleaching solutions constituting the invention may also contain bromides, such as potassium bromide, sodium bromide, ammonium bromide, or chlorides, such as rehalogens, such as potassium chloride, sodium chloride, ammonium chloride, etc. may contain a curing agent. The concentration of the rehalogenating agent is 0.1 to 5 mol, preferably 0.5 to 3 mol per j of bleaching solution.
It is a mole.

Moreover, it is preferable to use ammonium nitrate as a metal corrosion inhibitor.

In the case where the replenishment method is adopted in the present invention, the amount of replenishment of the bleaching solution is 200 ml or less, preferably 1
40~10IIl! It is.

Further, the bleaching treatment time is 120 seconds or less, preferably 60 seconds or less, and more preferably 50 seconds or less. The present invention is effective in such a shortened processing time.

In addition, during the treatment, iron(III) aminopolycarboxylate
It is preferable to aerate the bleaching solution using the complex salt to oxidize the produced aminopolycarboxylic acid iron (II) complex salt.

In the present invention, a photosensitive material that has been bleached with the bleaching solution as described above is then processed using a processing solution that has fixing ability.

Specific examples of such a processing liquid include a fixing liquid and a bleach-fixing liquid, which contain a fixing agent.

As fixing agents, thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate, thiocyanates (rodan salts) such as sodium thiocyanate, ammonium thiocyanate, potassium thiocyanate, thiourea, Thioether etc. can be used.

Among these, it is preferable to use a thiosulfate, especially ammonium thiosulfate, and more preferably a combination of a thiosulfate and a thiocyanate, particularly a combination of ammonium thiosulfate and ammonium thiocyanate.

When thiosulfate is used alone as a fixing agent, the amount is about 0.3 to 3 mol, preferably about 0.5 to 2 mol, per 11 of the fixing solution or bleach-fixing solution, and when thiocyanate is used alone, It is about 1 to 4 moles. In general, the amount of fixing agent, including when used in combination, is 0.3 to 5 mol, preferably 0.5 to 3.5 mol, per fixer or bleach-fixer.
It can be expressed in moles. However, when used together, the total amount may be within the above range.

In the present invention, in the most preferred combination of thiosulfate and thiocyanate, the thiosulfate is
~3 mol/2, thiocyanate 1 to 3 mol/j,
Preferably, it may be used at 1 to 2.5 mol/l.

Thus, fixing is promoted by including thiocyanate in the fixing solution or bleach-fixing solution. This effect of promoting retention has been known for some time (Gran
Modern Photography by T Haist
c Processing Volume 2 p171゜p583)
However, such effects can be greatly enhanced by adjusting the pH of the bleaching solution to the above range (pH 2.5 to 4.2).

In addition, if a conventional bleaching solution (about pH 5 to 6) is used and a fixing solution containing thiocyanate or a bleach-fixing solution is used for a short period of time, stains may occur on the surface of the photosensitive material (film). Although confirmed by the inventors,
It has also been found that by using the bleaching solution according to the invention, such problems are completely eliminated.

Therefore, the above effects can be obtained by setting the pH of the bleaching solution to the above range,
It can only be obtained by using a fixer or a fixer-bleaching solution containing thiocyanate, and cannot be obtained even if any of the requirements are missing.

Other compounds other than thiocyanate that can be used in combination with thiosulfate (especially ammonium thiosulfate) include thiourea, thioether (e.g. 3,6-dithia-
1,8-octanediol) and the like.

The amount of these compounds used in combination is generally about 0.01 to 0.1 mol per 1ffi of the fixing solution or bleach-fixing solution, but 1 to 3 mol may be used depending on the case.

The fixer or bleach-fixer contains sulfites as preservatives (e.g. sodium sulfite, potassium sulfite, ammonium sulfite) and hydroxylamine, hydrazine,
Bisulfite adducts of aldehyde compounds (eg, acetaldehyde sodium bisulfite) and the like can be included. Furthermore, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained, and in particular, preservatives are described in Japanese Patent Application No. 60-283881. It is preferable to use a sulfinic acid compound of

The bleach-fix solution may contain the above-mentioned known bleaching agents.

Preferred is aminopolycarboxylic acid ferric complex salt.

In the bleach-fix solution, the amount of bleach per 1 i of bleach-fix solution is from o, oi to 0.5 mol, preferably from 0.015 to 0.5 mol.
The amount is 0.3 mol, particularly preferably 0.02 to 0.2 mol.

In the present invention, the bleach-fix solution (mother liquor) at the start of processing is
It is prepared by dissolving the compound used in the above bleach-fix solution in water, but the bleach solution and fix solution prepared separately are mixed in 1F.
They may also be prepared by mixing. The pH of the fixer is 5.
-9 is preferable, and 7-8 is more preferable. Also,
The pH of the bleach-fix solution is preferably 6 to 8.5, more preferably 6.5 to 8.0.

When using the replenishment method, the amount of replenishment of fixer or bleach-fixer is 300 to 3000 m2 per 1 m2 of photosensitive material.
1 is preferable, but more preferably 300 to 1000 m!
It is.

Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixer and bleach-fixer for the purpose of stabilizing the solution.

Further, in the present invention, the total treatment time of the fixing treatment or the bleach-fixing treatment performed after the bleaching treatment is preferably 0.5 to 2 minutes, particularly 1 to 1.5 minutes.

The present invention is effective when applied to such short processing times.

The total processing time of the desilvering step of the present invention is short, and the effect of the water-sprinkling invention can be significantly obtained. The preferred time is 1 to 4 minutes.
More preferably, the time is 1 minute 30 seconds to 3 minutes. Further, the treatment temperature is 25 to 50°C, preferably 35 to 45°C.

In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step of the present invention, it is preferable that the stirring be as strong as possible in order to more effectively exhibit the effects of the present invention.

A specific method for strengthening stirring is disclosed in JP-A-62-18346.
No. 0, No. 62-183461, the method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material, and the method of colliding a jet of a processing liquid on the emulsion surface of a photosensitive material, as described in JP-A No. 62-183-1.
No. 83461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. method, and a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleaching agent and fixing agent into the emulsion film, and as a result increases the desilvering rate.

Further, the agitation improving means is more effective when a bleach accelerator is used, and can significantly increase the bleach accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

Typical desilvering treatment steps using a bleaching solution or a bleaching solution and a processing solution having a fixing ability (fixing solution, bleaching solution) in the present invention include the following.

■ Bleach-fixing ■ Bleach-bleach-fixing ■ Bleach → Washing with water ■ Rinse → Bleach-fixing ■ Bleaching → Bleach-fixing solution ■ Washing with water → Bleach-fixing solution Among the above steps, steps ■, ■, ■ Preferably, for step (1), for example, JP-A-61-75352
Disclosed in the issue.

In addition, even if the processing baths such as bleaching baths and fixing baths used in the above steps have a tank configuration of 2 or more tanks (for example, 2 to 4
(in this case a countercurrent system is preferred).

Among these, in the present invention, a process in which desilvering treatment is performed immediately after color development treatment is particularly preferred, and a remarkable effect is produced in such a case.

The present invention is usually carried out by applying an automatic developing machine, but
The automatic developing machine used in the present invention is JP-A-60-191
No. 257, No. 60-191258', No. 60-191
It is preferable to have the photosensitive material conveying means described in No. 259.

As described in JP-A-60-191257, such a conveying means can significantly reduce the amount of processing liquid brought into the post bath from the front bath, and is highly effective in preventing deterioration in the performance of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The effect of the present invention is remarkable when the total processing time (excluding drying time) is short, and specifically, the total processing time is 88%.
This effect is clearly exhibited when the processing time is less than 7 minutes, and the difference from conventional processing methods becomes even more remarkable when the processing time is 7 minutes or less. Therefore, in the present invention, the total treatment time is preferably 8 minutes or less, particularly preferably 7 minutes or less.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-I N,N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-[N-ethyl -N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethyl- N-[β
-(methanesulfonamide)ethylcoaniline D, -7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl- N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-ethoxydiethylniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxydiethylniline Among the above-mentioned -phenylenediamine derivatives, exemplified compound β-5 is particularly preferred.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. The amount of the aromatic primary amine color developing agent to be used is preferably about 0.03 to 0.03 kg per 1 j of color developing solution.
A concentration of about 20 g, more preferably about 0.5 to about log.

In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts are added to the color developing solution as preservatives as necessary. be able to.

The preferable amount of preservative added is 0.5 per 1e of color developer.
-10g, more preferably 1-5g.

Alternatively, the aromatic primary amine color developing agent may be directly applied to
Examples of compounds that maintain stability include various hydroxylamines, hydroxamic acids described in Japanese Patent Application No. 61-186559, hydrazines and hydrazides described in Japanese Patent Application No. 61-17075゜6, Japanese Patent Application No. 61-188742 and No. 61-2032.
It is preferable to add phenols described in No. 53, α-hydroxyketones and α-aminoketones described in No. 61-188741, and/or various saccharides described in No. 61-180816.

In addition, in combination with the above compounds, patent application No. 61-14782
No. 3, No. 61-166674, No. 61-165621
No. 61-164515, No. 61-170789 and No. 61-168159, etc.;

Diamines described in No. 61-188560, etc., No. 61
-165621, 61-169789 and 6
Polyamines described in No. 1-188619, No. 61-19
Nitroxy radicals described in No. 7760, No. 61-18
It is preferable to use the alcohols described in No. 6561 and No. 61-197419, the oximes described in No. 61-198987, and the tertiary amines described in No. 61-265149.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
- Salicylic acids described in No. 180588, JP-A-54-3
Alkanolamines described in No. 582, JP-A-56-9
Polyethyleneimines described in No. 4349, U.S. Patent No. 3
．． The aromatic polyhydroxy compound described in No. 746,544 and the like may be contained as necessary.

Particularly preferred is the addition of an aromatic polyhydroxy compound.

The color developing solution used in the present invention preferably has a pH of 9 to
12, more preferably 9 to ii, and o, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium phonate, potassium borate, Sodium tetraborate (borax) Potassium tetraborate, 0-
Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-2
-sodium hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of buffering agent added to the color developing solution is preferably O,1 mol/j or more, and particularly preferably O,1 to 0.4 mol/j.

In addition, various chelating agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or to improve the stability of the color developer.

The chelating agent is preferably an organic acid compound, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1.2- Diaminopropane tetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid,
2-phosphonobutane-1゜2.4-tricarboxylic acid, l
-hydroxyethylidene-1,1-diphosphonic acid, N,
N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid.

Two or more of these chelating agents may be used in combination, if necessary.

The amount of these chelating agents added may be sufficient to sequester metal ions in the color developing solution, for example, 1 to 10 g of O per lβ.

Any development accelerator can be added to the color developing solution if necessary. however.

The color developing solution in the present invention preferably does not substantially contain benzyl alcohol from the viewpoints of pollution, preparation properties, and prevention of color staining. Here, "substantially" means that the developer contains 2 ml or less, preferably not at all, per developer.

In addition, as a development accelerator, Japanese Patent Publication No. 37-16088
No. 37-5987, No. 38-7826, No. 44
-12380, 45-9019, U.S. Patent No. 3,
818,247, etc.; p-phenylenediamine compounds described in JP-A-52-49829 and JP-A-50-15554;
No. 137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 1977
Quaternary ammonium salts described in No. 6-156826, No. 52-43429, etc., U.S. Patent No. 2,494,903
No. 3,128,182, No. 4,230,79
No. 6, No. 3,253,919, Special Publication No. 41-114
No. 31, U.S. Patent No. 2,482,546, U.S. Patent No. 2,5
96,926, 3゜582.346, etc.; Japanese Patent Publication No. 37-16088, 42-
25201, U.S. Patent No. 3,128,183, Japanese Patent Publication No. 11431-1983, Japanese Patent Publication No. 42-23883, U.S. Patent No. 3,532,501, etc., and other l-phenyl-3-pyrazolidones. kind,
Imidazole and the like can be added as necessary.

In the present invention, any antifoggant can be further added as required. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, and 5-nitroisoindazole.
Nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole,
Representative examples include nitrogen-containing heterocyclic compounds such as hydroxyazaindolizine and adenine.

The color developing solution used in the present invention may contain a fluorescent whitening agent. As the fluorescent brightening agent, 4.4°-diamino-2,2°-disulfostilbene compounds are preferred. The amount added is 0 to 5 g/l, preferably 0. Ig~4g
/j.

Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature in the color developing solution in the present invention is 20 to 50°C.
, preferably 30 to 45°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes and 20 seconds. When a replenishment method is adopted, the replenishment amount is preferably small, but is 100 to 1500 Ilj, preferably 100 to 800 mg per 1 m'' of photosensitive material. More preferably 1
00 to 400 i.

Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment.

The processing method of the present invention can also be used for color reversal processing. The black-and-white developer used at this time is a so-called black-and-white first developer used in the commonly known reversal processing of color photosensitive materials. Various well-known additives that are used in black-and-white developing solutions used in processing solutions for black-and-white silver halide light-sensitive materials can be included in the black-and-white first developing solution for color reversal light-sensitive materials.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole,
Examples include water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds.

The processing method of the present invention includes processing steps such as color development, bleaching, bleach-fixing, and fixing as described above. Here, after the bleach-fixing or fixing process, processing steps such as washing with water and stabilization are generally carried out, but after processing with a processing solution that has fixing ability, washing with water is generally not necessary. It is also possible to use a simple treatment method in which stabilization treatment is not performed.

The rinsing water used in the rinsing step can contain known additives, if necessary.

For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, disinfectants that prevent the growth of various bacteria and algae, and antifungal agents (such as isothiazolones, organochlorine disinfectants, benzotriazole, etc.) etc.), a drying load, a surfactant to prevent unevenness, etc. can be used. Or L, E, West, “Water Q
ualityCriteria, Photo, Sci
, and Eng,, vol, 9°No, 6.
Compounds described in p. 344-359 (1965) and the like can also be used.

As the stabilizing liquid used in the stabilizing step, a processing liquid that stabilizes the dye image is used. For example, a solution having a buffering capacity of pH 3 to 6, a solution containing an aldehyde (for example, formalin), etc. can be used. The stabilizing liquid includes
Ammonium compounds, metal compounds such as Bi and An, optical brighteners, chelating agents (e.g. 1-hydroxyethylidene-1,1-diphosphonic acid), bactericides, as necessary.
A fungicide, a hardening agent, a surfactant, an alkanolamine, etc. can be used.

Further, the water washing step and the stabilization step are preferably performed by a multistage countercurrent method, and the number of stages is preferably 2 to 4 stages. The amount of replenishment is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

The water used in these washing steps or stabilization steps includes tap water, as well as Ca
, Mg concentration is 5mg/I! Deionized water,
It is preferable to use water that has been sterilized using halogen or ultraviolet germicidal lamps.

In each of the above processing steps for color photosensitive materials, when continuous processing is performed using an automatic processor, concentration of the processing solution may occur due to evaporation, especially when the processing amount is small or the opening area of the processing solution is large. It becomes noticeable. In order to correct such concentration of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid from the water washing step or the stabilization step flows into a pre-bath having a fixing ability.

The light-sensitive material in the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of the emulsion layers and non-photosensitive layers.

A typical example is a silver halide color photographic light-sensitive material that has a light-sensitive layer on a support, which is composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different light sensitivities. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in multilayer silver halide color photographic light-sensitive materials, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are installed in this order from the body side. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different color-sensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

For the middle class, JP-A-61-43748 and JP-A-59-11
No. 3438, No. 59-113440, No. 61-200
It may contain a coupler DIR compound as described in No. 37 and No. 61-20038, and it may also contain a color mixing inhibitor, an ultraviolet absorber, an anti-stinting agent, etc. as commonly used. good.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are
West German Patent No. 1,121,470 or British Patent No. 9
As described in No. 23,045, a two-layer structure consisting of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer can be preferably used.

Usually, it is preferable to arrange the halogen emulsion layers so that the photosensitivity decreases in order toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.

Also, JP-A-57-112751, JP-A No. 62-2003
No. 50, No. 62-206541, No. 62-20654
As described in No. 3, etc., a low-sensitivity emulsion layer may be provided on the side away from the support, and a high-sensitivity/high-density emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) /high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitive layer (RL)/in order,
Alternatively, they can be installed in the order of B H/B L/G L/G H/RH/RL, or in the order of BH/BL/GH/GL/RL/RH.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
They can also be arranged in the order of H/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in this order from the farthest side from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is a silver halide emulsion layer with higher sensitivity than the middle layer. An example is an arrangement consisting of three layers having different photosensitivity, in which a silver halide emulsion layer with low photosensitivity is disposed, and the photosensitivity gradually decreases toward the support. Even in a case where the emulsion layer is composed of three layers with different sensitivities, as described in JP-A No. 59-202464, the medium-sensitivity emulsion layer is separated from the side far from the support in the same color-sensitive layer. /high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

Any of these layer arrangements can be used in the color photosensitive material of the present invention, but in the present invention, the dry film thickness of all the constituent layers of the color photosensitive material excluding the support and the undercoat layer and back layer of the support is 20.0μ or less. It is preferable to achieve the object of the present invention. More preferably 1
It is 8.0μ or less.

These film thickness regulations are determined by the color developing agent incorporated into these layers of the color photosensitive material during and after processing, and the amount of remaining color developing agent has a large effect on staining that occurs during image storage after processing. It depends.

In particular, the increase in color of magenta, which is thought to be caused by the green-sensitive color layer, is greater than the increase in color of other cyan and yellow colors.

Note that the lower limit value in the film thickness regulation is desirably reduced from the above regulation to a range that does not significantly impair the performance of the photosensitive material. The lower limit of the total dry film thickness of the constituent layers of the photosensitive material excluding the support and the undercoat layer of the support is 12.0μ, and the lower limit of the total dry film thickness of the constituent layers excluding the support and the undercoat layer of the support is 12.0 μm. The lower limit of the total dry film thickness of the constituent layers is ], Oμ
It is.

Further, the film thickness may be reduced in either the photosensitive layer or the non-photosensitive layer.

The film thickness of the multilayer color photosensitive material in the present invention is measured by the following method.

The photosensitive material to be measured is stored at 25° C. and 50% RH for 7 days after its preparation. First, measure the total thickness of this photosensitive material, then remove the coated layer on the support, measure the thickness again, and use the difference to determine the total thickness of the photosensitive material excluding the support. The film thickness shall be . This thickness can be measured using, for example, a film thickness measuring device using a contact type electric conversion element (AnrLtus Electric Co., Lt.
d.

K-402B 5tand). Note that the coating layer on the support can be removed using an aqueous sodium hypochlorite solution.

Next, using a scanning electron microscope, take a cross-sectional photograph of the photosensitive material (magnification is preferably 3.000 times or more), measure the total thickness on the support and the thickness of each layer, and calculate the previous film thickness. Measured value of total thickness by measuring device (absolute value of actual thickness)
The thickness of each layer can be calculated by comparing the

Swelling rate of the photosensitive material in the present invention [(25°C, equilibrium swelling film thickness in H, O - dry total film thickness at 25°C, 55% RH/dry total film thickness at 25°C, 55% RH)] x100] is 5
0 to 200% is preferable, and 70 to 150% is more preferable.

If the swelling ratio deviates from the above value, the amount of color developing agent remaining will increase, and this will have an adverse effect on photographic performance, image quality such as desilvering properties, and film properties such as film strength.

Furthermore, the swelling rate of the photosensitive material in the present invention is defined as the saturated swelling rate, which is 90% of the maximum swollen film thickness reached when processed in a color developing solution (38°C, 3 minutes 15 seconds).
When the time required to reach a film thickness of 2 is defined as the swelling rate Tl/2, it is preferable that Tl/2 is 15 seconds or less. More preferably Tl/2 is 9 seconds or less.

The preferred silver halide contained in the photographic emulsion layer of the color light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol % or less of silver iodide.

Particularly preferred is silver iodobromide containing from about 2 to about 25 mole percent iodide.

Silver halide grains in photographic emulsions include those with regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. It may be one having crystal defects or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (RD) No. 17.
643 (December 1978) pp. 22-23, “1
．． Emulsion preparation
nand types)” and the same No. 18716
(November 1979) 648 pages, “Physics and Chemistry of Photography” by Grafkide, published by Paul Montell (P, Glafkide)
fkides.

Chimie et Physique Photog
raphique paul montel, 1967
), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G, F, Duffin.

Photographic Emulsion Che
a+1stry (FocalPress, 1966
), Zelikman et al., “Production and Coating of Photographic Emulsions”, published by Focal Press (V.L., Zelikman et a.
l、Making and CoatingPhoto
graphic emulsion, Focal
Press, 1964).

U.S. Patent No. 3,574,628, U.S. Patent No. 3°655.3
Monodisperse emulsions such as those described in No. 94 and British Patent No. 1,413.748 are also preferred.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described in Photographic Science and Engineering by Gutoff.

Photographic 5science and
Engineering), Volume 14, 248-257
(1970); U.S. Patent No. 4,434,226;
4,414.310, 4,430,048, 4,439,520 and British Patent No. 2゜11
It can be easily prepared by the method described in No. 2.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a phase structure. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization.

Additives used in such processes are listed in Research Disclosure No. 17643 and Research Disclosure No. 1871.
6, and the relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

RD No. 17643 Chemical sensitizer page 23 Sensitivity enhancer Spectral sensitizer, pages 23-24 Super sensitizer RD No. 18716 Page 648 Right column Same as above Page 648 Right column - Page 649 Right column Brightener Page 24 Anti-fog Agents, pages 24-25 Stabilizers Light absorbers, pages 25-26 Filter dyes, UV absorbers Anti-stain agents Dye Image stabilizers Hardeners Binder Plasticizers, Lubricant Coating aids, Surface active agents Page 25 Right column 25 Page 2ε Page 26 Page 27 Pages 26-27 Page 649 Right column Page 649 Right column ~ Page 650 Left column Page 650 Left to right column Page 651 Left column Same as above Page 650 Right column Same as above Static Page 27 Same as above The present invention includes various features. A color coupler can be used, and a specific example thereof is the above-mentioned RD No. 17643, ■-〇-
It is described in the patent described in G.

As a yellow coupler, for example, U.S. Patent No. 3,93
3.501, No. 4,022,620, No. 4,32
No. 6,024, No. 4,401.752, No. 4,2
48.961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425.020, British Patent No. 1,476.760,
U.S. Patent No. 3,973,968, U.S. Patent No. 4,314.0
No. 23, No. 4.511,649, European Patent No. 249
, No. 473A, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 10,619, No. 4,351,897, European Patent No. 73,636, U.S. Patent No. 3,081,432,
No. 3.725,064, RD No. 24220 (1
June 984), JP-A No. 60-33552, RD No.
, 24230 (June 1984) JP-A-60-436
No. 59, No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951,
U.S. Patent No. 4,500,630, U.S. Patent No. 4,540゜6
No. 54, No. 4,556,630, WO (PCT) 8
Particularly preferred are those described in No. 8104795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,21.
No. 2, No. 4,146.396, No. 4,228,2
No. 33, No. 4゜296.200, No. 2,369,
No. 929, No. 2,801,171, No. 2,772
．． No. 162, No. 2,895,826, No. 3,77
No. 2,002, No. 3,758,308, No. 4,3
34. Of No. 1, No. 4゜327.173, West German Patent Publication No. 3,329.729, European Patent No. 121,3
No. 65A, No. 249,453A, U.S. Patent No. 3゜4
No. 46.622, No. 4,333,999, No. 4,
No. 753.871, No. 4,451.559, No. 4
, No. 427,767, No. 4.690,889, No. 4. -254,212, same No. 4,296,199,
Preferred are those described in JP-A-61-42658 and the like.

Colored couplers for correcting unnecessary absorption of color-forming dyes are disclosed in RD No. 17643, Section 1-G, and US Patent No. 4.
No. 163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. ．． 138,258
Preferred are those described in British Patent No. 1,146,368. Additionally, there are couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling, as described in U.S. Pat. No. 4,774,181, and U.S. Pat.
It is also preferred to use a coupler having as a leaving group a dye precursor group which reacts with a developing agent to form a dye as described in No. 77.120.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4.366.237 and British Patent No. 2,125.
, 570, European Patent No. 96.570, and German Patent Publication No. 3,234.533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,576.910, British Patent No. 2,102
, No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor has the aforementioned RD No. 17.
643, the patent described in Sections 4 to F, JP-A-57-15
No. 1944, No. 57-154234, No. 60-184
No. 248, No. 63-37346, U.S. Patent No. 4.24
Those described in No. 8,962 and No. 4,782.012 are preferred.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2097.140,
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130.427, U.S. Pat. No. 4,283,472, U.S. Pat. Long equivalent couplers described in JP-A No. 4,310.618, etc. DIR redox compound releasing couplers described in JP-A-60-185950, JP-A-62-24252, etc. DIR coupler-releasing couplers DI
RIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. i73,302
Coupler R that releases a dye that recovers color after separation as described in item A
DNo. 11449, 24241. Unexamined Japanese Patent Publication 1986-20
Bleach accelerator-releasing couplers described in US Pat. No. 4,553,477, etc., leuco dye-releasing couplers described in JP-A-63-75747, etc. US Pat. No. 4,774 Examples include couplers that emit fluorescent dyes as described in , No. 181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high-boiling point solvents used in the oil-in-water dispersion method are described in U.S. Patent No. 2,322,027, etc.; Specific examples of organic solvents include phthalate esters (
Dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate,
bis(2,4-di-t-amylphenyl) phthalate,
bis(2,4-di-t-amyl phenyl) inphthalate, bis(1゜1-diethylpropyl) phthalate, etc.) Phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl) Phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-ethylhexyl phenyl phosphonate, etc.) Benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, etc.).

2-ethylhexyl-p-hydroxybenzoate, etc.) Amides (N,N-diethyldodecanamide, N,
N-diethyl laurylamide, N-tetradecylpyrrolidone, etc.) Alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acids, esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctyl citrate, etc.) Aniline derivatives (N.

N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. In addition, as an auxiliary solvent, those with a boiling point of about 30°C or higher,
Preferably, an organic solvent having a temperature of 50° C. or more and about 160° C. or less can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat.
No. 541,230, etc.

These couplers can also be impregnated into rhodapuru latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of high-boiling organic solvents as described above.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. Wo 8810 O723 are used. In particular, the use of acrylamide-based polymers is preferred from the viewpoint of color image stabilization.

The present invention can be applied to various color photosensitive materials. It is particularly preferable to apply the present invention to color negative films for general use or movies, and color reversal films for slides or televisions.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D No. 17643 page 28 and same No. 18716
It is described from the right column on page 647 to the left column on page 648.

<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 On a subbed cellulose triacetate film support,
A sample of a multilayer color photosensitive material consisting of each layer having the composition shown below was prepared.

(Composition of the photosensitive layer) The numbers for each component indicate the coating weight in g/m2. However, for silver halide, colloidal silver and couplers, the amounts are expressed in g/m2 of silver, and for sensitizing dyes, the amounts are expressed in moles per mole of silver halide in the same layer. () at the end of each layer
The numerical value written inside indicates the film thickness [unit: μ].

1st layer: Black colloidal silver gelatin V-1 V-2 cpci-1 olv-I olv-2 olv-3 Silver coating amount 0.20 1.90 0.10 0.20 0.05 0. 01 0.01 0.08 (2,0) 2nd layer: Intermediate layer fine grain silver bromide (equivalent sphere diameter 0.07μ) Silver coating amount 0.15 Gelatin 0.90Cpd-2
0,20 (0,9) Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high Ag
Type I, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%,
(Tedecahedral grains) Silver coating amount 0.50 Silver iodobromide emulsion (AgI 4.0 mol%.

Internal high AgI type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particle) Silver coating amount 0.40 Gelatin 1.90E x S
-19,OX 10-'Mole Ex S -23,O
X 10-molEx S -30,8X to-'molEx S-40,6X 10-'molEx C
-10,33 ExC-20,009 ExC-30,028 ExC-60,14 4th N: Second red-sensitive emulsion layer Silver iodobromide emulsion (AgI 16 mol%, internal high AgI type 1 sphere equivalent) Diameter 1.oμ, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/thickness ratio 4.0) Gelatin xS-I xS-2 xS-3 xS-4 xC-3 xC-4 xC-6 Silver type Cloth 1 o, g.

1.20 4, OX 10-'mol 1.5X 10"'mol 0.4X 10-'mol 0.4X 10"'mol 0.05 0.10 0.08 (1,4) Fifth layer: 3 red-sensitive emulsion layer silver iodobromide emulsion (AgI 10.6 mol%, internal high Ag
L type, equivalent sphere diameter 1.2μ, coefficient of variation of equivalent sphere diameter 28%,
Plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount 1. lO Gelatin 1.00ExS-1
2,5810-' mole Ex S -20,7X 10-' mole Ex S
-30,3 0,10 (1,0) Seventh layer: First green-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high Ag
Type I 1 ball equivalent diameter 0.7 μ 1 ball equivalent diameter coefficient of variation 14%,
Tedecahedral grains) Silver coating amount 0.20 Silver iodobromide emulsion (AgI 4.0 mol%, internal high Agl
Type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 22%, 1
Tetrahedral particles) Silver coating amount 0. lO gelatin l, 30E x S
-55x 10-'mol ExM-62x 10-'molExM-7LX 10-'molExM-10,21 ExM-60,31 ExM-20,10 ExM-50,03 Solv-10,20 Solv -50,03 (1,8) 8th layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high iodine type, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 25% , plate-shaped particles, diameter/thickness ratio 3.0) Gelatin xS-5 xS-6 xS-7 xM-I E x M-3 olv-I olv-5 Silver coating amount 0.50 0.45 4.5X 10 -'mol 1.8 Emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high Ag
Type I, equivalent sphere diameter 1.2μ, coefficient of variation of equivalent sphere diameter 28%,
Plate-shaped particles, diameter/thickness ratio 6.0) Gelatin xS-5 xS-6 xS-7 xM-3 xM-4 xM-I xC-4 olv- Silver coating amount 1.20 1.20 2.4X 10- 'Mole 1, OX 10-'Mole 1, OX 10-'Mole 0.01 0.14 0.04 0,005 0.2 (1,6) 11th layer: Yellow filter layer pd-3 Gelatin olv-1 0,05 0,50 0,10 (0,5) 12th layer: Intermediate layer gelatin 0.05 pd-2 0,10 (0,5) 13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high Ag
Type I, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%,
Tedecahedral grains) Silver coating amount 0.15 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI
Type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 22%, 1
Tetrahedral particles) Silver coating amount 0.08 Gelatin 1.00E x S
-84,5x 10-'mol ExY-10,62 ExY-20,02 S o 1 v -10,20 (1,7) 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 19. 0 mol%, internal high Ag
Type I, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 16%,
Tedecahedral particles) Silver coating amount 0.80 Gelatin 0.30E x S
-83,Ox 10-'molExY-10,22S o 1v -10,07 (0,71 15th layer: Intermediate layer fine grain silver iodobromide (AgI 2 mol%, uniform type, equivalent sphere diameter 0. 13μ) Silver coating amount 0.20 Gelatin 0.26 (0,3) 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high Ag
Type I, equivalent sphere diameter 1.5 μ, coefficient of variation of equivalent sphere diameter 28%,
Plate-shaped particles, diameter/thickness ratio 5.0) Silver coating amount 1.20 Gelatin 0.80E x S
-81,8 0,01 (1,5) 18th layer: 2nd protective layer Fine grain silver iodobromide (equivalent sphere diameter 0.07μ) Silver coating amount 0.
18 Gelatin 0.90
Polymethyl methacrylate particles (diameter 1.5μ) 0.20 W-10,20 H-10,40 Cpd -51,00 V-1 H x/y=7/3 (weight ratio) V-2 xM-3 xC-1 IJ xC-2 xC-3 r elbow ExC-4 n14 ExC-5 ExC-6 xM-1 E xM-2 t xM-4 xM-5 xM-6 xY-1 xY-2 xS -1 ExS-2 ExS-3 ExS-4 C,H.

Robbery 2H6 ExS-5 ExS-6 ExS-7 ExS-8 olv-1 olv-2 C2H.

olv-3 olv-5 pd-1 pd-2 TomoH pd-3 pd-4 pci-s -1 CsF+ tSOJHCHjJAzCHzOCH2a(
zN' (CH3) z-1 CI4. =CH5O□CH2C0N)I-CH2cH,
=coso,a(,coN)l-co.

At this time, the dried film thickness of the support of the prepared sample and all coating layers excluding the undercoat layer of the support was 21.9μ.

The prepared sample was cut and processed into a width of 35 mm, subjected to wet exposure to sunlight (color temperature of the light source: 4800''K), and processed using a cine-type automatic processor in the processing steps shown below.

Processing process Processing time Processing temperature Color development
3 minutes 15 seconds 37.8℃ bleaching
40 seconds 38.0℃ fixation
1 minute 30 seconds 38.0℃ water washing (1)
30 seconds 38.0℃ water washing (2) 30 seconds 38.0℃ stable 30 seconds
Dry at 38.0℃ for 1 minute
The 55° C. water washing was carried out in a countercurrent manner from (2) to (1), and the crossover time was 5 seconds in both cases, and this time was included in the treatment time of the previous step.

The composition of the treatment liquid is shown below. As a bleaching agent in a bleaching solution, the redox potential of 1,3-propylenediaminetetraacetic acid ferric ammonium hydrate is 250 as described above.
mV.

(Color developer) Unit (g) Diethylenetriaminepentaacetic acid 1゜01-Hydroxyethylidene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 2-Methyl-4-[N-ethyl-N -(β-Hydroxyethyl)aminocoaniline sulfate 4.5 Add water 1.01H 3,0 4,0 30,0 1,4 1,5mg 2.4 10.05 (Bleach solution) 1.3 -Propylene diamic acid ferric ammonium acetate monohydrate 1.3 -Propylene diamic acid acetate ammonium bromide ammonium nitrate Acetic acid (98%) Add water to pH [adjust with aqueous ammonia (27%)] (Fixer) Ethylene diamine tetra Diammonium acetate salt Ammonium sulfite Ammonium thiosulfate (700 g/l) Aqueous solution Silver bromide Ammonium iodide units (g) 144.0 2.8 84.0 30.0 50.0 1.0 (Table 1 Units (g) 1 .7 14.0 240.0II11 0.9 Add water to 1.0R pH 7.0 (washing water) Tap water was mixed with H-type strongly acidic cationic steel pipe resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type Strongly basic anion exchange resin (Amberlite IRA-40
Water is passed through a hotbed column filled with 0) to reduce the concentration of calcium and magnesium ions to 3 mg/j or less,
Then sodium dichloride isocyanurate 20 tag/
R and 150 mg of sodium sulfate were added.

The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizer) Unit (g) Formalin (37%) 1.2mg Surfactant
0,4[C1oHa+-0+cH2CHi
o+IoH1 ethylene glycol 1.0
Add water 1. atpH5.0
~7.0 The treatments as described above are designated as treatments IA to IE (Table 1) depending on the pH of the bleach solution used.

D□ measured with green light (G light) from the characteristic curves obtained by measuring the concentration of the samples treated by treatments 1A to IE. Read each value.

Further, the bleaching solution was changed to the following treatment solution formulation, the bleaching treatment time was changed to 6 minutes and 30 seconds, and the treatment was carried out without changing anything else.

(Standard bleaching solution) Unit (g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 1O90 Ammonium bromide 140.0 Ammonium nitrate
30.0 Ammonia water (27%) 6.5m
j Water was added and the pH was 1.01 pH 6.0 The D7° value was determined in the same manner as above for the sample treated using this standard bleaching solution. Based on this D mln
It's called value.

This standard Do. Using this value as a standard, the increase in the D mln value from the standard D mln value in Processes 1A to IE was evaluated as bleaching fog.

The bleaching fog is shown in Table 1 in relation to the p)l value of the bleaching solution used.

Table 1 Processing bleach solution pH value Bleach Blade IA (present invention) 1B (present invention) IC (present invention) 10 (comparison) IE (comparison) 3.0 +0.013.6
+Q, Q14.0
+0.024.4
+0.085.0 +0.25
As shown in Table 1, bleach fog was significantly reduced in treatments 1A, IB, and IC in which the pH of the bleach solution was within the range of the present invention. In particular, it can be seen that the reduction is much greater than in the treatment IE in which a bleaching solution closest to the pH conventionally considered to be preferable is applied.

Further, in the treatments IA, IB, and IC of the present invention, there was no occurrence of desilvering defects, and the photographic properties were at a satisfactory level.

Example 2 In treatments IA, IB, and IC1IE of Example 1, the 1,3-PDTA-Fe (III) complex salt of the bleaching solution was
, 3-PDTA-Fe (III) complex salt and ED'TA-
Fe(■) complex salt (oxidation-reduction potential 110 mV) at a molar ratio of 1
Processes 2A, 2B, 2C, and 2E (Table 2) correspond to processes IA, IB, and IC1IE, respectively, and are processed in the same manner, except that the combination use of process IA, IB, and IC1IE is changed.

Samples treated with each of these treatments were examined for the occurrence of bleaching edge burrs and defective desilvering (defects in bleaching).

Bleaching defects were evaluated by measuring the amount of residual silver (μg/cm'') in the maximum image density area (D, □) using a fluorescent X-ray method.

The results are shown in Table 2.

Table 2 (μg/am”) 2A (present invention) 3.0 5 +0
．． 012B (present invention) 3.6 5
→Q, Q12C (present invention) 4.0 6
+0.022E (comparison) 5.0
30 +0.12 Example 3 1°3-PDTA in the bleach solution in Process IB of Example 1
-Fe(III) complex salt, 1,4-butylenediaminetetraacetic acid/Fe(III) complex salt, (redox potential 230
m”/), N-(2-acetamido)iminodiacetic acid/Fe(III) complex salt (redox potential 180 mV) or EDTA-Fe(III) [salt (redox potential 110 mV) was used in the same manner. The processed ones are referred to as processing 3B-1, 3B-2, and 3B-3, respectively.

In treatment 3B-3, in which EDTA-Fe (III) complex salt was used as the oxidizing agent and a bleaching solution of pH 3.6, no bleach fog occurred, but the amount of residual silver in 111 parts of D was 39. The silver content was as high as 5 ug/cm2, and the desilvering property was poor.

On the other hand, in treatments 3B-1 and 3B-2 using a high potential oxidizing agent, results similar to those in treatment IB were obtained.

From this, it was confirmed that desilvering failure and bleaching fog can be solved at the same time only when the high potential oxidizing agent of the present invention is used at a low pH.

Example 4 Processing IA-IH of Example 1 was performed in the same manner except that the fixing time was changed to 1 minute.
1 to 4E-1 (Table 3).

In addition, in Processes 4A-1 to 4E-1, the same processes were performed except that 160 g/j of ammonium thiocyanate was added to the fixing solution, and Processes 4A-2 to 4E-2 (Table 3) ).

Samples treated with each of these treatments were examined for occurrence of desilvering failure (fixing failure).

Regarding defective desilvering, the amount of residual silver in the unexposed area (μg/cm
”) was evaluated by measuring with the fluorescence X II method.

In addition, stains on the surface of the photosensitive material (film) after processing were visually observed.

These results are shown in Table 3.

In addition, in the table, ○ and △ are shown for the film surface.
, indicated by ×.

○...No stains △...Stains occur on 1/3 or less of the film surface ×...
Stains occur on more than 1/3 of the film surface. As shown in Table 3, when processing with a bleaching solution having a pH value within the range of the present invention, in combination with a fixing solution containing thiocyanate, further desorption can be achieved. It is possible to speed up silver processing (
Processing 4A-2, 4B-2, 4C-2) In addition, there was no staining on the film surface, which was a problem in conventional rapid processing using a thiocyanate-containing fixer, and good photographic properties were obtained. Ta.

<Effects of the Invention> According to the present invention, it is possible to speed up the desilvering process,
The occurrence of bleach fog is suppressed.

Furthermore, when a processing liquid containing thiocyanate and having a fixing ability is used, even faster processing is possible and no staining occurs on the surface of the photosensitive material.

Claims (2)

[Claims] (1) After imagewise exposure of the silver halide color photographic light-sensitive material,
In a processing method in which a color development process is performed with a color developer containing an aromatic primary amine color developing agent, and then a bleaching process is performed with a bleaching solution, the bleaching solution has an oxidation-reduction potential of 150
Contains an oxidizing agent of mV or more, and the pH of this bleaching solution is 2.
．． 5 to 4.2. A method for processing a silver halide color photographic light-sensitive material. (2) The method for processing a silver halide color photographic material according to claim 1, wherein after bleaching with the bleaching solution, processing is performed with a processing solution having a fixing ability and containing thiocyanate as a fixing agent.